Paraffinic jet and diesel fuels and base oils from vegetable oils via a combination of hydrotreating, paraffin disproportionation and hydroisomerization

ABSTRACT

The present invention relates to a new process which comprises the steps of hydrotreating, paraffin disproportionation and hydroisomerization to convert biological hydrocarbonaceous oxygenated oils comprising triglycerides into biologically-derived paraffinic jet/diesel fuels, solvents and base oils. A combination of conventional hydrogenation/dehydrogenation catalysts, such as Pt/Al 2 O 3 , and conventional olefin metathesis catalysts, such as WO 3 /SiO 2 , or inexpensive variations thereof, is generally employed in the paraffin disproportionation step.

This application claims the benefit of provisional Application No.61/754,375, filed Jan. 18, 2013, herein incorporated in its entirety.

FIELD OF THE INVENTION

The present invention relates to a new process which comprises the stepsof hydrotreating, paraffin disproportionation and hydroisomerization toconvert biological hydrocarbonaceous oxygenated oils comprisingtriglycerides into biologically-derived paraffinic jet and diesel fuels,solvents and base oils.

BACKGROUND OF THE INVENTION

Biological products are in demand to replace those made from petroleumand other non-renewable resources. Biological resources, however, havevery different compositions and properties in comparison to petroleum.Novel methods of making the products in demand from biological resourcesare therefore required.

Triglycerides from vegetable oils such as soybean oil and canola oil area particular type of biological resource and one type of biologicalhydrocarbonaceous oxygenated oil. These can be either fats or oils. Theyare composed of a glycerol backbone esterified with three fatty acids.The fatty acids can be either saturated or unsaturated. The fatty acidstypically contain straight hydrocarbonaceous chains with between 6 and24 carbon atoms per molecule. Each biological resource providestriglycerides composed of fatty acids with chains containing only a fewnarrowly defined numbers of carbon atoms. When these fatty acids areconverted into paraffins, the distribution of the resulting paraffins isoften narrow in terms of the length of the molecular chains (i.e., thecarbon atom number per molecule), and inconsistent with the intendedproduct use, e.g., for jet and diesel fuels, solvents and base oils.

Biological triglycerides can be hydrogenated to form paraffins, andthese paraffins typically fall in the boiling range of diesel or jetfuel. In this aspect, U.S. Patent Application Publication No2004/0230085 teaches a process for saturation of triglycerides, butemploys an isomerization catalyst. The product contains 73 wt %iso-paraffins and only 13% n-paraffins. This process also does notdescribe how to make lighter paraffins useful as biologically-derivedparaffinic solvents, or how to make heavier paraffins useful asbiologically-derived paraffinic base oils.

Molecular Redistribution is a technique of paraffin disproportionationthat can redistribute a paraffin feed into its lighter and heavieranalogues with a broader boiling range centered at the same averagemolecular weight. Such a process is disclosed in U.S. Pat. No.6,566,569, which employs a feedstock composed predominantly of pentanes.The entire disclosure is incorporated by reference in this application.There is no teaching in the patent, however, of the use of triglyceridesas a feedstock. Furthermore, there has been no teaching of theproduction of biologically-derived paraffinic jet and diesel fuels,biologically-derived paraffinic solvents or biologically-derivedparaffinic base oils.

SUMMARY OF THE INVENTION

A process for preparing a paraffin product stream from feed comprisingtriglycerides is disclosed. The process involves contacting atriglyceride feedstock with a catalyst that includes a hydrotreatingcatalyst under conditions which hydrogenate the fatty acids of thetriglycerides to long chain paraffins having a narrow boiling range,followed by contacting the resulting paraffins with a paraffindisproportionation catalyst to broaden the boiling range of the paraffinproducts. The paraffin disproportionation catalysts such as MolecularRedistribution catalysts have a hydrogenation/dehydrogenation componentas well as an olefin metathesis component, for creation of lighter andheavier analogues of the feed paraffins. In the paraffindisproportionation reactions, the feed paraffins are firstdehydrogenated to their corresponding olefins over thehydrogenation/dehydrogenation component of the catalyst. These olefinsare then metathesized to their lighter and heavier analogues over theolefin metathesis component of the catalyst. The resulting olefins arethen hydrogenated to their corresponding paraffins. This processprovides a paraffin product stream which may possess carbon chains inthe range from 2 through approximately 40 carbon atoms.

In one embodiment, the present invention provides a process for themanufacture of biologically-derived paraffinic jet and diesel fuels,solvents and base oils from a biological hydrocarbonaceous oxygenatedoil, comprising triglycerides, comprising: (a) hydrotreating thebiological hydrocarbonaceous oxygenated oil to form a first effluentmixture comprising propane, carbon monoxide, carbon dioxide, water and an-paraffinic product; (b) recovering the n-paraffinic product from thefirst effluent mixture; and (c) converting the n-paraffinic product ofstep (b) over a paraffin disproportionation catalyst to form a secondeffluent mixture comprising a light n-paraffinic biologically derivedproduct and a heavy n-paraffinic biologically derived product.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is gas chromatographic data of the products produced viaMolecular Redistribution of n-hexadecane (top, Example 4) and n-eicosane(bottom, Example 5) at 650° F., 1000 psig and 0.5 LHSV.

FIG. 2 is a gas chromatographic data of the feed (top) and product(bottom) produced via Molecular Redistribution of a mixture ofn-hexadecane, n-heptadecane, n-octadecane, n-nonadecane and n-eicosaneat 650° F., 1000 psig and 0.5 LHSV (Example 6).

FIG. 3 is a gas chromatographic data of the product produced viaMolecular Redistribution of n-hexadecane at 750° F., 500 psig and 0.5LHSV (Example 7). Top: feed; bottom: product.

FIG. 4 is the distillation data (boiling point vs. volume %) of the feedand product produced via Molecular Redistribution of n-hexadecane at750° F., 500 psig and 0.5 LHSV (Example 7), as determined by thesimulated distillation (ASTM D-2887 which is based on gaschromatography).

FIG. 5 (top) shows the gas chromatographic data of the hydrotreatingproduct produced from soybean oil in Example 8 at 600° F., 1000 psig, ahydrogen gas rate of 8.0 MSCF/bbl and an LHSV of 1.0 h⁻¹. FIG. 5(bottom) shows the gas chromatographic data of the product produced inExample 9 via Molecular Redistribution of the above hydrotreatingproduct of soybean oil at 750° F., 500 psig and 0.5 LHSV.

FIG. 6 is the distillation data (boiling point vs. volume %) of (a) thehydrotreating product produced from soybean oil in Example 8 at 600° F.,1000 psig, a hydrogen gas rate of 8.0 MSCF/bbl and an LHSV of 1.0 h⁻¹and (b) the product produced in Example 9 via Molecular Redistributionof the above hydrotreating product of soybean oil at 750° F., 500 psigand 0.5 LHSV, as determined by the simulated distillation (ASTM D-2887which is based on gas chromatography).

FIG. 7 (top) shows the gas chromatographic data of thehydrotreating-hydroisomerization product produced from Canola oil inExample 10 at 1000 psig, a hydrogen gas rate of 5.0 MSCF/bbl and a totalLHSV of 0.35 h⁻¹. FIG. 7 (bottom) shows the gas chromatographic data ofthe product produced in Example 11 via Molecular Redistribution of thehydrotreating-hydroisomerization product of Canola oil at 750° F., 500psig and 0.5 LHSV.

FIG. 8 is the distillation data (boiling point vs. volume %) of (a) thehydrotreating-hydroisomerization product produced from Canola oil inExample 10 at 1000 psig, a hydrogen gas rate of 5.0 MSCF/bbl and a totalLHSV of 0.35 h⁻¹ and (b) the product produced in Example 11 viaMolecular Redistribution of the above hydrotreating-hydroisomerizationproduct of Canola oil at 750° F., 500 psig and 0.5 LHSV, as determinedby the simulated distillation (ASTM D-2887 which is based on gaschromatography).

DETAILED DESCRIPTION OF THE INVENTION

In some embodiments, the present invention provides a process for themanufacture of biologically-derived paraffinic jet and diesel fuels,solvents and base oils from a biological hydrocarbonaceous oxygenatedoil, further comprising: (d) recovering the light n-paraffinicbiologically derived product from step (c); and (e) recovering the heavyn-paraffinic biologically derived product from step (c).

In some embodiments, the present invention provides a process for themanufacture of biologically-derived paraffinic jet and diesel fuels,solvents and base oils from a biological hydrocarbonaceous oxygenatedoil, further comprising an isomerization step of the first effluentmixture from step (b).

In some embodiments, the present invention provides a process for themanufacture of biologically-derived paraffinic jet and diesel fuels,solvents and base oils from a biological hydrocarbonaceous oxygenatedoil, further comprising an isomerization step of the second effluentmixture from step (c).

In some embodiments, the present invention provides a process for themanufacture of biologically-derived paraffinic jet and diesel fuels,solvents and base oils from a biological hydrocarbonaceous oxygenatedoil, further comprising an isomerization step of the light n-paraffinicbiologically derived product, heavy n-paraffinic biologically derivedproduct, or both the light and heavy paraffinic biologically derivedproducts.

In some embodiments, the present invention provides the triglyceride isa mixture of triglycerides.

In some embodiments, the present invention provides the biologicalhydrocarbonaceous oxygenated oil is selected from the group consistingof rapeseed oil, colza oil, canola oil, tall oil, sunflower oil, soybeanoil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanutoil, castor oil, coconut oil, lard, tallow and train oil.

In some embodiments, the present invention provides a process for themanufacture of biologically-derived paraffinic jet and diesel fuels,solvents and base oils from a biological hydrocarbonaceous oxygenatedoil, wherein step (c) further comprises: treatment of the n-paraffinicproduct of step (b) with a hydrogenation/dehydrogenation catalyst and anolefin metathesis catalyst under conditions which dehydrogenate theparaffins to olefins, metathesize the olefins, and hydrogenate theolefins to paraffins to provide a third effluent mixture comprising alight n-paraffinic biologically derived product and a heavy n-paraffinicbiologically derived product.

In some embodiments, the present invention provides ahydrogenation/dehydrogenation catalyst includes at least one metal or acorresponding metal compound selected from the group consisting of iron,cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium andplatinum.

In some embodiments, the present invention provides ahydrogenation/dehydrogenation catalyst comprises a metal orcorresponding metal compound selected from the group consisting of:rhenium, tin, germanium, gallium, indium, lead, tin and mixturesthereof.

In some embodiments, the present invention provides an olefin metathesiscatalyst comprises a metal or corresponding metal compound is selectedfrom the group consisting of tungsten, molybdenum, tin and rhenium.

In some embodiments, the present invention provides an olefin metathesiscatalyst comprises tungsten.

In some embodiments, the present invention provides ahydrogenation/dehydrogenation catalyst comprises platinum or a platinumcompound and the olefin metathesis catalyst comprises tungsten.

In some embodiments, the present invention provides ahydrogenation/dehydrogenation catalyst is platinum-on-alumina and theolefin metathesis catalyst is tungsten-on-silica and the volumetricratio of the platinum component to the tungsten component is greaterthan 1:50 and less than 50:1, and

wherein the amount of platinum on the alumina is within the range offrom about 0.01 weight percent to about 10 weight percent on anelemental basis and the amount of tungsten on the silica is within therange of from about 0.01 weight percent to about 50 weight percent on anelemental basis.

In some embodiments, the present invention provides a volumetric ratioof the platinum component to the tungsten component is between 1:10 and10:1 and wherein the amount of platinum on the alumina is within therange of from about 0.1 weight percent to about 5.0 weight percent on anelemental basis and the amount of tungsten on the silica is within therange of from about 0.1 weight percent to about 20 weight percent on anelemental basis.

In some embodiments, the present invention provides that step (c)further comprises a temperature between about 400° F. to 1000° F.

In some embodiments, the present invention provides that step (c)further comprises a pressure between about 50 psig to 3000 psig.

In some embodiments, the present invention provides that step (c)further comprises a liquid hourly space velocity between about 0.1 to 5h⁻¹.

In some embodiments, the present invention provides that step (a)further comprises a temperature for hydrotreating between about 300° F.to 750° F.

In some embodiments, the present invention provides that step (a)further comprises a total reaction pressure for hydrotreating betweenabout 50 to 3000 psig.

In some embodiments, the present invention provides that step (a)further comprises a liquid hourly space velocity for hydrotreatingbetween about 0.1 to 5 h⁻¹.

In some embodiments, the present invention provides that step (a)further comprises a hydrogen feed rate for hydrotreating between about0.1 to 20 MSCF/bbl.

In some embodiments, the present invention provides a temperature forthe isomerization between about 200° F. to 900° F.

In some embodiments, the present invention provides total reactionpressure for the isomerization between about 15 to 3000 psig.

In some embodiments, the present invention provides a liquid hourlyspace velocity for the isomerization between about 0.1 and about 5 h⁻¹.

In some embodiments, the present invention provides a hydrogen feed ratefor the isomerization between about 0.1 to 30 MSCF/bbl.

In some embodiments, the present invention provides a biologicalhydrocarbonaceous oxygenated oil will not include appreciable amounts(i.e., amounts that would adversely affect the catalyst used forparaffin disproportionation) of hydrogen, alkenes, alkynes, thiols,amines, water, air, oxygenates or cycloparaffins.

In some embodiments, the present invention provides an n-paraffinicproduct comprising at least 90 wt % n-paraffins.

In its broadest aspect, the present invention is directed to anintegrated process for producing paraffinic product streams varying inmolecular chain length from a feedstock that includes triglycerides. Theprocess involves obtaining an appropriate triglyceride feedstock,hydrotreating the triglycerides to form n-paraffins, dehydrogenating then-paraffins to create olefins, metathesizing the resulting olefins, andhydrogenating the resulting metathesized olefins to form paraffins whichare the lighter and heavier analogues of the starting n-paraffins. Thedehydrogenation, metathesis and hydrogenation steps preferably occur inthe same reactor. All steps also preferably occur in the same reactor.The process described herein is an integrated process. As used hereinthe term “integrated process” refers to a process which involves asequence of steps, some of which may be parallel to other steps in theprocess, but which are interrelated or somehow dependent upon eitherearlier or later steps in the total process.

An advantage of the present process is the effectiveness and relativelyinexpensive processing costs with which the present process may be usedto prepare high quality components for incorporation into jet fuel anddiesel compositions. In particular, an advantage is that feedstocks thatare not conventionally recognized as suitable sources for such productstreams can be used.

Feedstocks for the Hydrotreating Reaction

As the feedstock, a biological raw material containing fatty acidsand/or fatty acid esters that originate from plants, animals or fish isused, said biomaterial being selected from the group consisting ofvegetable oils and fats, animal fats, fish oils and mixtures thereof.Examples of suitable biomaterials are wood-based and other plant-basedfats and oils such as rapeseed oil, colza oil, canola oil, tall oil,sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil,mustard oil, palm oil, peanut oil, castor oil, coconut oil, as well asfats contained in plants bred by means of gene manipulation,animal-based fats such as lard, tallow, train oil, and fats contained inmilk as well as recycled fats of the food industry and mixtures of theabove.

The basic structural unit of a typical vegetable or animal fat useful asthe feedstock is a triglyceride. Specifically, the triglyceride is atriester of glycerol with three fatty acid molecules, having thestructure presented in the following formula I:

“Triglyceride” refers to class of molecules having the general formula(I):

wherein R, R¹ and R² are independently aliphatic residues having from 6to 24 carbon atoms (e.g., from 8 to 20 carbon atoms, or from 10 to 16carbon atoms). The term “aliphatic” means a straight (i.e., un-branched)or branched, substituted or un-substituted hydrocarbon chain that iscompletely saturated or that contains one or more unsaturatedcarbon-carbon bonds. The fatty acid composition may vary considerably infeedstocks of different origin.

Hydrotreating Chemistry and Catalysts

The term “hydrotreating” is given its conventional meaning and describesprocesses that are well known to those skilled in the art. Hydrotreatingrefers to a catalytic process, usually carried out in the presence offree hydrogen, in which the primary purpose is the desulfurization,denitrification and/or deoxygenation of the feedstock. Generally, inhydrotreating operations, cracking of the hydrocarbon molecules, i.e.,breaking the larger hydrocarbon molecules into smaller hydrocarbonmolecules is minimized and the unsaturated hydrocarbons are either fullyor partially hydrogenated.

Catalysts used in carrying out hydrotreating operations are well knownin the art. See, for example, see U.S. Pat. Nos. 4,347,121 and 4,810,357for general descriptions of hydrotreating, and some typical catalystsused in hydrotreating processes. The hydrotreating catalyst can be a“supported catalyst” which refers to a catalyst in which the activecomponents, e.g., Group VIII and Group VIB metals or compounds thereof,are deposited on a carrier or support. Alternatively, it can be a“self-supported catalyst”. “Self-supported catalyst” can be usedinterchangeably with “unsupported catalyst,” or “bulk catalyst,” meaningthat the catalyst composition is NOT of the conventional catalyst formwhich has a preformed, shaped catalyst support which is then loaded withmetal compounds via impregnation or deposition. In one embodiment, theself-supported catalyst is formed through precipitation. In anotherembodiment, the self-supported catalyst has a binder incorporated intothe catalyst composition. In yet another embodiment, the self-supportedcatalyst is formed from metal compounds and without any binder.

“Catalyst precursor” in one embodiment refers to a compound containingat least a metal selected from Group IIA, Group IIB, Group IVA, GroupVIII metals and combinations thereof (e.g., one or more Group IIAmetals, one or more Group IIB metals, one or more Group IVA metals, oneor more Group VIII metals, and combinations thereof); at least a GroupVIB metal; and, optionally, one or more organic oxygen-containingpromoters, and which compound can be used directly in the upgrade of arenewable feedstock (as a catalyst), or can be sulfided for use as asulfided hydroprocessing catalyst.

“Group IIA” or “Group IIA metal” refers to beryllium (Be), magnesium(Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), andcombinations thereof in any of elemental, compound, or ionic form.

“Group IIB” or “Group IIB metal” refers to zinc (Zn), cadmium (Cd),mercury (Hg), and combinations thereof in any of elemental, compound, orionic form.

“Group IVA” or” “Group IVA metal” refers to germanium (Ge), tin (Sn) orlead (Pb), and combinations thereof in any of elemental, compound, orionic form.

“Group VIB” or “Group VIB metal” refers to chromium (Cr), molybdenum(Mo), tungsten (W), and combinations thereof in any of elemental,compound, or ionic form.

“Group VIII” or “Group VIII metal” refers to iron (Fe), cobalt (Co),nickel (Ni), ruthenium (Ru), rhodium (Ro), palladium (Pd), osmium (Os),iridium (Ir), platinum (Pt), and combinations thereof in any ofelemental, compound, or ionic form.

The Periodic Table of the Elements refers to the version published bythe CRC Press in the CRC Handbook of Chemistry and Physics, 88th Edition(2007-2008). The names for families of the elements in the PeriodicTable are given here in the Chemical Abstracts Service (CAS) notation.

“Noble metal” refers to a metal selected from ruthenium, rhodium,palladium, silver, osmium, iridium, platinum, and gold.

“Promoter” refers to an organic agent that interacts strongly withinorganic agents (either chemically or physically) in a reaction to forma catalyst or a catalyst precursor, leading to alterations in thestructure, surface morphology and composition, which in turn results inenhanced catalytic activity.

“Presulfiding” or “presulfided” refers to the sulfidation of a catalystprecursor in the presence of a sulfiding agent such as H₂S or dimethyldisulfide (DMDS) under sulfiding conditions, prior to contact with afeedstock in an upgrade process.

Promoted Catalyst—Self-Supported Catalyst:

In one embodiment, the catalyst for the upgrade of renewable feedstockis a promoted self-supported catalyst derived from a catalyst precursor.The catalyst precursor can be a hydroxide or oxide material, preparedfrom at least a Group VIB metal precursor feed and at least anothermetal precursor feed. The at least another metal precursor can be usedinterchangeably with M^(P), referring to a material that enhances theactivity of a catalyst (as compared to a catalyst without the at leastanother metal, e.g., a catalyst with just a Group VIB metal), with thepromoter being present in an amount of at least 0.05 to about 5 molartimes of the total number of moles of the metals of Group VIB and atleast another metal present, e.g., a Group VIII metal. In oneembodiment, the promoter is present in an amount of up to 1000 molartimes the total number of moles of the metals.

The self-supported or unsupported catalyst precursor made can beconverted into a hydroconversion catalyst (becoming catalyticallyactive) upon sulfidation. However, the self-supported catalyst precursorcan be used in the conversion of the renewable feedstock by itself (as acatalyst), or it can be sulfided prior to use, or sulfided in-situ inthe presence of sulfiding agents in the reactor. In one embodiment, theself-supported catalyst precursor is used un-sulfided, with or withoutany addition of sulfiding agents (e.g., H₂S) to the reactor system orinherent in the feed, even for the hydroconversion of a feedstockconsisting essentially of renewable materials (without any sulfurpresent in the feed as sulfiding agent). In one embodiment, aself-supported multi-metallic oxide may also be used. The self-supportedmulti-metallic oxide comprises at least one Group VIII metal and atleast two Group VIB metals. In one embodiment, the ratio of Group VIBmetal to Group VIII metal in the precursor ranges from about 10:1 toabout 1:10. In another embodiment, the oxide catalyst precursor isrepresented by the formula: (X)_(b)(Mo)_(c)(W)_(d)O_(f), wherein X is Nior Co, Mo is molybdenum, W is tungsten, the molar ratio of b: (c+d) is0.5:1 to 3:1 (e.g., 0.75:1 to 1.5:1, or 0.75:1 to 1.25:1), the molarratio of c: d is >0.01:1 (e.g., greater than 0.1:1, 1:10 to 10:1, or 1:3to 3:1), and f=[2b+6 (c+d)]/2. The oxide catalyst precursor furthercomprises one or more promoters L. In one embodiment, the self-supportedcatalyst precursor is of the formula (NiL)_(x)(Mo_(y)W_(1-y))O_((x+3));wherein L refers to one or more promoters; and wherein x:(1-y) is1.7-2.4; and y is 0.25 to 0.67. The oxide precursor is generated bycombining the Group VIB and group VIII metals, forming a product, thensubsequently calcining the product formed thereof.

In another embodiment, the catalyst precursor is in the form of ahydroxide compound, comprising at least one Group VIII metal and atleast two Group VIB metals. In one embodiment, the hydroxide catalystprecursor is represented by the formula: A_(v)[(M^(P))(OH)_(x)(L)^(n)_(y)]_(z)(M^(VIB)O₄), wherein A is one or more monovalent cationicspecies; M^(P) has an oxidation state (P) of either +2 or +4 dependingon the metal(s) being employed; L is one or more oxygen-containingpromoters, and L has a neutral or negative charge n≦0; M^(VIB) is atleast a Group VIB metal having an oxidation state of +6; M^(P):M^(VIB)has an atomic ratio between 100:1 and 1:100; v−2+P*z−x*z+n*y*z=0; and0<v≦2; 0<x≦P; 0<y≦−P/n; 0<z. In one embodiment, the catalyst precursoris charge-neutral, carrying no net positive or negative charge.

In one embodiment, A is selected from the group consisting of an alkalimetal cation, an ammonium cation, an organic ammonium cation and aphosphonium cation.

In one embodiment, M^(P) has an oxidation state of either +2 or +4.M^(P) is at least one of a Group IIA metal, Group IIB metal, Group IVAmetal, Group VIII metal and combinations thereof. In one embodiment,M^(P) is at least a Group VIII metal with M^(P) having an oxidationstate P of +2. In another embodiment, M^(P) is selected from Group IIBmetals, Group IVA metals and combinations thereof. In one embodiment,M^(P) is selected from the group of Group IIB and Group VIA metals suchas zinc, cadmium, mercury, germanium, tin or lead, and combinationsthereof, in their elemental, compound, or ionic form. In anotherembodiment, M^(P) is a Group IIA metal compound, selected from the groupof magnesium, calcium, strontium and barium compounds. M^(P) can be insolution or in partly in the solid state, e.g., a water-insolublecompound such as a carbonate, hydroxide, fumarate, phosphate, phosphite,sulfide, molybdate, tungstate, oxide, or mixtures thereof.

In one embodiment, the promoter L has a neutral or negative charge n≦0.Examples of promoters L include but are not limited to carboxylates,carboxylic acids, aldehydes, ketones, the enolate forms of aldehydes,the enolate forms of ketones, and hemiacetals; organic acid additionsalts such as formic acid, acetic acid, propionic acid, maleic acid,malic acid, cluconic acid, fumaric acid, succinic acid, tartaric acid,citric acid, oxalic acid, glyoxylic acid, aspartic acid, alkane sulfonicacids such as methanesulfonic acid and ethanesulfonic acid, arylsulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acidand arylcarboxylic acids; carboxylate containing compounds such asmaleate, formate, acetate, propionate, butyrate, pentanoate, hexanoate,dicarboxylate, and combinations thereof.

In one embodiment, M^(VIB) is at least a Group VIB metal having anoxidation state of +6. In another embodiment, M^(VIB) is a mixture of atleast two Group VIB metals, e.g., molybdenum and tungsten. M^(VIB) canbe in solution or in partly in the solid state. In one embodiment,M^(P):M^(VIB) has a mole ratio of 10:1 to 1:10.

In one embodiment, the self-supported catalyst is prepared from a mixedmetal sulfide (“MMS”) catalyst precursor, characterized by having anoptimized Ni:Mo:W composition with a molar ratio of Ni/W of 1.62 Ni/W2.5, a molar ratio of W/Mo is in the range of 0.5≦W/Mo≦6.0, and a molarratio of Ni/(Mo+W) in the range of 0.57<Ni/(Mo+W)<2.1. In anotherembodiment, the MMS catalyst precursor comprises nickel, molybdenum andtungsten having relative proportions within a compositional rangedefined by four points ABCD in a ternary phase diagram, with molarfractions of the four points ABCD defined by A(Ni_(x)=0.36, Mo_(x)=0.41,W_(x)=0.22); B(Ni_(y)=0.45, Mo_(y)=0.36, W_(y)=0.18); C(Ni_(z)=0.58,Mo_(z)=0.06, W_(z)=0.36), and D (Ni_(w)=0.68, Mo_(w)=0.05, W_(w)=0.27).The MMS catalyst precursor can be used for the upgrade of the renewablefeedstock directly with or without being pre-sulfided, or with orwithout any sulfiding agents being present or added to the feedstock.Further details regarding the description of the catalyst precursor andthe self-supported catalyst formed thereof are described in a number ofpatents and patent applications, including U.S. Pat. Nos. 6,156,695;6,162,350; 6,274,530; 6,299,760; 6,566,296; 6,620,313; 6,635,599;6,652,738; 6,758,963; 6,783,663; 6,860,987; 7,179,366; 7,229,548;7,232,515; 7,288,182; 7,544,285, 7,615,196; 7,803,735; 7,807,599;7,816,298; 7,838,696; 7,910,761; 7,931,799; 7,964,524; 7,964,525;7,964,526; 8,058,203; and U.S. Patent Application Publication Nos.2007/0090024, 2009/0107886, 2009/0107883, 2009/0107889 and 2009/0111683,the relevant disclosures are included herein by reference.

Embodiments of the process for making the self-supported catalystprecursor are as described in the references indicated above, andincorporated herein by reference. In one embodiment, the first step is amixing step wherein at least one Group VIB metal precursor feed and atleast one another metal precursor feed are combined together in aprecipitation step (also called co-gelation or co-precipitation),wherein a catalyst precursor is formed as a gel. The precipitation (or“co-gelation”) is carried out at a temperature and pH under which theGroup VIB metal compound and at least another metal compound precipitate(e.g., forming a gel). In one embodiment, the temperature is from 25° C.to 350° C. and the pressure is from 0 to 3000 psig (0 to 20.7 MPagauge). The pH of the reaction mixture can be changed to increase ordecrease the rate of precipitation (co-gelation), depending on thedesired characteristics of the catalyst precursor product, e.g., anacidic catalyst precursor. In one embodiment, the mixture is left at itsnatural pH during the reaction step(s). The pH is maintained in therange from 3-9 in one embodiment; and from 5-8 in a second embodiment.

Promoted Catalyst—Supported Catalyst:

In another embodiment, the hydrotreating catalyst is selected fromsupported catalysts suitable for hydroconversion of renewablefeedstocks. Such catalysts comprise at least one metal componentselected from Group VIII metals and/or at least one metal componentselected from the Group VIB metals. Group VIII metals include iron (Fe),cobalt (Co) and nickel (Ni). Noble metals, such as palladium (Pd) and/orplatinum (Pt), can be included in the hydrotreating catalyst. Group VIBmetals include chromium (Cr), molybdenum (Mo) and tungsten (W). GroupVIII metals can present in the catalyst in an amount of from 0.5 to 25wt. % (e.g., from 2 to 20 wt. %, 3 to 10 wt. %, 5 to 10 wt. %, or 5 to 8wt. %) and Group VIB metals can be present in the catalyst in an amountof from 0.5 to 25 wt. % (e.g., from 5 to 20 wt. %, or 10 to 15 wt. %),calculated as metal oxide(s) per 100 parts by weight of total catalyst,where the percentages by weight are based on the weight of the catalystbefore sulfiding. The total weight percent of metals employed in thehydrotreating catalyst is at least 5 wt. % in one embodiment. Theremainder of the catalyst can be composed of the support material,although optionally other components may be present (e.g., filler,molecular sieve, or the like, or a combination thereof).

The metal components in the supported catalyst can be in the oxideand/or the sulfide form. If a combination of at least a Group VIII and aGroup VIB metal component is present as (mixed) oxides, it can besubjected to a pre-sulfiding treatment prior to proper use inhydroprocessing. Suitably, the catalyst usually comprises one or morecomponents of Ni and/or Co and one or more components of Mo and/or W.However, the supported catalyst precursor can be used in the conversionof the renewable feedstock by itself (unsulfided and as a catalyst) withor without any addition of sulfiding agents (e.g., H₂S) to the reactorsystem or inherent in the feed, or it can be pre-sulfided prior to use,or sulfided in-situ in the presence of sulfiding agents in the reactoror in the feed.

The supported catalyst can be prepared by blending, or co-mulling,active sources of the aforementioned metals with a binder. Examples ofbinders include silica, silicon carbide, amorphous and crystallinesilica-aluminas, silica-magnesias, aluminophosphates, boria, titania,zirconia, and the like, as well as mixtures and co-gels thereof.Preferred supports include silica, alumina, alumina-silica, and thecrystalline silica-aluminas, particularly those materials classified asclays or zeolitic materials. Especially preferred support materialsinclude alumina, silica, and alumina-silica, particularly either aluminaor silica. Other components, such as phosphorous, can be added asdesired to tailor the catalyst particles for a desired application.These support materials may be either naturally occurring or in the formof gelatinous precipitates or gels including mixtures of silica andmetal oxides. Naturally occurring clays which can be composited with thecatalyst include those of the montmorillonite and kaolin families. Theseclays can be used in the raw state as originally mined or initiallysubjected to calumniation, acid treatment or chemical modification. Theblended components can then shaped, such as by extrusion, dried andcalcined at temperatures up to 1200° F. (649° C.) to produce thefinished catalyst. Alternatively, other methods of preparing theamorphous catalyst include preparing oxide binder particles, such as byextrusion, drying and calcining, followed by depositing theaforementioned metals on the oxide particles, using methods such asimpregnation. The supported catalyst, containing the aforementionedmetals, can then further dried and calcined prior to use as ahydrotreating catalyst.

The support materials can be of many types including some that haveacidic catalytic activity. Ones that have activity include amorphoussilica-alumina or may be a zeolitic or non-zeolitic crystallinemolecular sieve. Examples of suitable matrix molecular sieves includezeolite Y, zeolite X and the so-called ultra stable zeolite Y and highstructural silica:alumina ratio zeolite Y such as that described in U.S.Pat. Nos. 4,401,556, 4,820,402 and 5,059,567. Small crystal size zeoliteY, such as that described in U.S. Pat. No. 5,073,530, can also be used.Non-zeolitic molecular sieves which can be used include, for example,silicoaluminophosphates (SAPO), ferroaluminophosphate, titaniumaluminophosphate, and the various ELAPO molecular sieves described inU.S. Pat. No. 4,913,799 and the references cited therein. Detailsregarding the preparation of various non-zeolite molecular sieves can befound in U.S. Pat. No. 5,114,563 (SAPO); U.S. Pat. No. 4,913,799 and thevarious references cited in U.S. Pat. No. 4,913,799. Mesoporousmolecular sieves can also be used, for example the M41S family ofmaterials (J. Am. Chem. Soc. 1992, 114, 10834-10843), MCM-41 (U.S. Pat.Nos. 5,246,689, 5,198,203 and 5,334,368), and MCM-48 (Kresge et al.,Nature 359 (1992) 710).

In one embodiment, the supported catalyst is a hydroprocessing catalystprepared as disclosed in US20090298677A1, the relevant disclosures areincluded herein by reference, by depositing onto a carrier having awater pore volume a composition comprising at least a Group VIB metaland at least a Group VIII metal of the Periodic Table of the Elements,optionally a phosphorus-containing acidic component, and at least apromote, deposited onto a carrier having a water pore volume, and thencalcining the impregnated carrier at a temperature greater than 200° C.and lower than the decomposition temperature of the promoter. The GroupVIB metal in one embodiment is selected from molybdenum Mo and tungstenW. The Group VIII metal is selected from cobalt Co and nickel Ni. Thepromoter is present in an amount of 0.05 to about 5 molar times of thetotal number of moles of the metals of Group VIB and Group VIII. In oneembodiment, the molar ratio of the Group VIII metal to Group VIB metalis about 0.05 to about 0.75.

In one embodiment, the promoter is selected from the group ofhydroxycarboxylic acids, ethylene glycol, glycerol, ethanolamine,polyethylene glycol, hydroquinone, ethylenediamine,ethylenediamine-tetraacetic acid, cysteine, alanine, methionine,gluconic acid, pyridine-2,3-dicarboxylic acid, thiophene-2-carboxylicacid, mercaptosuccinic acid, nicotinic acid, lactose, andacetone-1,3-dicarboxylic acid. In another embodiment, the promoter isselected from hydroxycarboxylic acids such as tartaric acid, malic acid,glyceric acid, citric acid and gluconic acid. In yet another embodiment,the promoter is citric acid.

In one embodiment, the supported catalyst has an average pore size of 1to 10 nm (e.g., from 5 to 10 nm) and a surface area of from 20 to 400m²/g (e.g., from 100 to 300 m²/g).

Reactor System:

The hydroprocessing process for the upgrade of the renewable feedstockcan be a single-staged or multiple-staged reactor system. In oneembodiment, the process utilizes a single-stage system. The reactorsystem can be of any reactor type. In one embodiment, the feedstock isprocessed in a fixed bed reactor. In one embodiment, unreactedtriglycerides can be recycled to the reactor of the single-stagedreactor system (having only one reactor) or to one of the reactors inthe multiple-staged reactor system (having multiple reactors) forfurther processing to maximize production of the desired product(s).

In one embodiment, the reactor system comprises at least two reactors inseries with the different reactors employing the same or differentcatalysts. In another embodiment, the reactor comprises a single reactorhaving at least two catalyst zones, with the different catalyst zonesemploying the same or different catalysts. In a third embodiment, thesystem is a single reactor containing a single catalyst type, aself-supported catalyst or a supported catalyst.

In one embodiment of a reactor system employing different catalysts, thedifferent catalysts are employed in a layered or stacked bed reactorsystem. By “layered” or “stacked bed,” it is meant that the firstcatalyst appears in a separate catalyst layer, bed, reactor, or reactionzone, and the second catalyst appears in a separate catalyst layer, bed,reactor, or reaction zone downstream, in relation to the flow of thefeed, from the first catalyst. In one embodiment of a stacked bedsystem, the system comprises about 5-95 vol. % of the first catalystwith the second catalyst comprising the remainder. In a secondembodiment, the volume ratio of the first catalyst is about 30-60 vol.%. In a third embodiment, the volume ratio of the first catalyst rangesfrom 5 to about 50 vol. %. In one embodiment of a stacked bed system,the first catalyst is a supported catalyst, and the second catalyst is aself-supported catalyst.

Hydroprocessing Conditions:

The hydroprocessing conditions can be selected so that an overallconversion rate of triglycerides in the feedstock is at least 20 wt. %,(e.g., at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or 95wt. %). Suitable hydroprocessing conditions can include a temperature offrom 302° F. to 752° F. (150° C. to 400° C.), e.g., from 383° F. to 464°F. (195° C. to 240° C.), 491° F. to 662° F. (255° C. to 350° C.), orfrom 491° F. to 563° F. (255° C. to 295° C.); a total reaction pressureof from 50 to 3000 psig (0.35 to 20.7 MPa gauge), e.g., from 800 to 2000psig (5.5 to 13.8 MPa gauge), or from 1600 to 2000 psig (11.0 to 13.8MPa gauge); a liquid hourly space velocity (LHSV) of from 0.1 to 5 h⁻¹,e.g., from 0.5 to 2 h⁻¹; and a hydrogen feed rate of from 0.1 to 20MSCF/bbl (thousand standard cubic feet per barrel), e.g., from 1 to 10MSCF/bbl. Note that a feed rate of 10 MSCF/bbl is equivalent to 1781 LH₂/L feed. In one embodiment, the hydroprocessing conditions include areaction temperature of at least 446° F. (230° C.) and a reactionpressure from 50 to 3000 psig (0.35 to 20.7 MPa gauge) for the liquideffluent having a normal paraffins concentration of at least 90 wt. %.

Paraffin Disproportionation Chemistry and Catalysts

As used herein, “paraffin disproportionation” is a process in which asingle paraffin, a mixture of isomeric paraffins, and/or a mixture ofparaffins and/or isoparaffins with a narrow molecular weight range isconverted into a mixture that includes lighter and heavier paraffinsthan those in the starting paraffin or paraffinic mixture. “MolecularRedistribution” is one of these processes.

Molecular Redistribution typically uses a combination of conventionalhydrogenation/dehydrogenation catalysts, such as Pt/Al₂O₃, andconventional olefin metathesis catalysts, such as WO₃/SiO₂, orinexpensive variations thereof. The chemistry does not require usinghydrogen gas, and therefore does not require relatively expensiverecycle gas compressors. The chemistry is typically performed at mildpressures (100-3000 psig). The chemistry is typically thermoneutral and,therefore, there is no need for expensive reactor quench systems orinterstage reheaters to control the temperature.

Depending on the nature of the catalysts, Molecular Redistributioncatalysts may be sensitive to impurities in the feedstock, such asnitrogen and sulfur-containing compounds and moisture, and these mayneed to be removed prior to the reaction. The presence of excess olefinsand hydrogen in the Molecular Redistribution zone are also known toaffect the equilibrium of the Molecular Distribution reaction and maypossibly deactivate the catalyst. Since the composition of the fractionsmay vary, some routine experimentation will be necessary to identify thecontaminants that are present and identify the optimal processing schemeand catalyst to use in carrying out the invention.

Molecular Redistribution, as described herein, generally involves twodistinct chemical reactions. First, the paraffins are converted intoolefins on the hydrogenation/dehydrogenation catalyst in a process knownas dehydrogenation or unsaturation. The resulting olefins aremolecularly redistributed, or disproportionated, into lighter andheavier olefins by a process known as olefin metathesis upon contactingthe metathesis catalyst. The metathesized olefins are then convertedinto paraffins in a process known as hydrogenation or saturation uponcontact with the hydrogenation/dehydrogenation catalyst. For example, aC₅ containing feedstock is molecularly redistributed, ordisproportionated, to produce a product stream that includes C⁴⁻ and C₆₊hydrocarbons.

Various catalysts are known to catalyze the Molecular Redistributionreaction. The catalyst used to carry out the present invention has bothhydrogenation/dehydrogenation activity and olefin metathesis activity.The dehydrogenation activity is believed to be necessary to convert theparaffins to olefins, which are believed to be the actual species thatundergo olefin metathesis to make olefins lighter and heavier than thestarting olefins. Following olefin metathesis, the olefin is convertedback into a paraffin. It is theorized that thehydrogenation/dehydrogenation activity of the catalyst also contributesto rehydrogenation of the olefin to a paraffin. While it is not intendedthat the present invention be limited to any particular mechanism, itmay be helpful in explaining the choice of catalysts to further discussthe sequence of chemical reactions which are believed to be responsiblefor Molecular Redistribution of the paraffins. As an example, thegeneral sequence of reactions for pentane is believed to be:

C₅H₁₂

C₅H₁₀+H₂

2C₅H₁₀

C₄H₈+C₆H₁₂

C₄H₈+C₆H₁₂+2H₂

C₄H₁₀C₆H₁₄

The hydrogenation/dehydrogenation catalyst will typically include aGroup VIII metal from the Periodic Table of the Elements, which includesiron, cobalt, nickel, palladium, platinum, rhodium, ruthenium, osmium,and iridium. To minimize the acid-catalyzed reactions such as crackingor coke formation, the acidity of the hydrogenation/dehydrogenationcatalyst is often adjusted or eliminated by adding some Group IA or IIAmetal cations such as Li⁺¹, Na⁺¹ or Mg⁺².

Platinum and palladium or the compounds thereof are preferred forinclusion in the hydrogenation/dehydrogenation component, with platinumor a compound thereof being especially preferred. As noted previously,when referring to a particular metal in this disclosure as being usefulin the present invention, the metal may be present as elemental metal oras a compound of the metal. As discussed above, reference to aparticular metal in this disclosure is not intended to limit theinvention to any particular form of the metal unless the specific nameof the compound is given, as in the examples in which specific compoundsare named as being used in the preparations.

Usually, the olefin metathesis catalyst will include one or more of ametal or the compound of a metal from Group VIB or Group VIIB of thePeriodic Table of the Elements, which include chromium, manganese,molybdenum, rhenium and tungsten. Molybdenum, rhenium, tungsten, andcompounds including these metals are preferred for including in theMolecular Redistribution catalyst. Tungsten and compounds includingtungsten are particularly preferred. The metals described above may bepresent as elemental metals or as compounds including the metals, suchas, for example, metal oxides. The metals may be present on the catalystcomponent either alone or in combination with other metals.

In most cases, the metals in the catalyst mass will be supported on arefractory material. Refractory materials suitable for use as a supportfor the metals include conventional refractory materials used in themanufacture of catalysts for use in the refining industry. Suchmaterials include, but are not necessarily limited to, alumina,zirconia, silica, boria, magnesia, titania and other refractory oxidematerial or mixtures of two or more of any of the materials. The supportmay be a naturally occurring material such as clay, or syntheticmaterials such as silica-alumina and borosilicates. Molecular sievessuch as zeolites also have been used as supports for the metals used incarrying out the dual functions of the catalyst mass. See, for example,U.S. Pat. No. 3,668,268. Mesoporous materials such as MCM-41 and MCM-48,such as described in Kresge, C. T., et al., Nature (Vol. 359) pp.710-712, 1992, may also be used as a refractory support. Other knownrefractory supports such as carbon may also serve as a support for theactive form of the metals in certain embodiments. The support ispreferably non-acidic, i.e., having few or no free acid sites on themolecule. Free acid sites on the support may be neutralized by means ofalkali metal salts, such as those of lithium. Alumina, particularlyalumina on which the acid sites have been neutralized by an alkali saltsuch as lithium nitrate, is usually preferred as a support for thehydrogenation/dehydrogenation component, and silica is usually preferredas the support for the metathesis component.

The amount of active metal present on the support may vary, but it mustbe at least a catalytically active amount, i.e., a sufficient amount tocatalyze the desired reaction. In the case of thehydrogenation/dehydrogenation component, the active metal content willusually fall within the range from about 0.01 weight percent to about 50weight percent on an elemental basis, with the range of from about 0.1weight percent to about 20 weight percent being preferred. For themetathesis component, the active metals content will usually fall withinthe range of from about 0.01 weight percent to about 50 weight percenton an elemental basis, with the range of from about 0.1 weight percentto about 25 weight percent being preferred.

A typical catalyst for use in the processes described herein includes aplatinum component and a tungsten component as described in U.S. Pat.No. 3,856,876, the entire disclosure of which is herein incorporated byreference. In one embodiment of the present invention, the catalystincludes a mixture of platinum-on-alumina and tungsten-on-silica,wherein the volumetric ratio of the platinum component to the tungstencomponent is greater than 1:50 and less than 50:1. Preferably thevolumetric ratio of the platinum component to the tungsten component inthis particular embodiment is between 1:10 and 10:1. In one embodiment,both the hydrogenation/dehydrogenation component and the olefinmetathesis component are present within the catalyst mass on the samesupport particle as, for example, a catalyst in which thehydrogenation/dehydrogenation component is dispersed on an unsupportedolefin metathesis component such as tungsten oxide. However, in analternative embodiment, the catalyst components are separated ondifferent particles.

In a reactor having a layered fixed catalyst bed, the two componentsmay, in such an embodiment, be separated in different layers within thebed. However, separate reactors may be used for carrying out thedehydrogenation and olefin metathesis steps. In processing schemes wherethe dehydrogenation of the paraffins to olefins occurs separately fromthe olefin metathesis reaction, it may be necessary to include anadditional hydrogenation step in the process, since the rehydrogenationof the olefins must take place after the olefin metathesis step.

The process conditions selected for carrying out the present inventionwill depend upon the Molecular Redistribution catalysts used. Ingeneral, the temperature in the reaction zone will be within the rangeof from about 400° F. (200° C.) to about 1000° F. (540° C.) withtemperatures in the range of from about 500° F. (260° C.) to about 850°F. (455° C.) usually being preferred. The pressure in the reaction zoneshould be maintained above 100 psig, and preferably the pressure shouldbe maintained above 500 psig. The maximum practical pressure for thepractice of the invention is about 3000 psig. The feedstock to theMolecular Redistribution preferably should contain no added hydrogen.

In the event the catalyst deactivates with the time-on-stream, specificprocesses that are well known to those skilled in art are available forthe regeneration of the catalysts.

Different reactor types can be used, such as fixed bed, fluidized bed,ebullated bed, etc. An example of a suitable reactor is a catalyticdistillation reactor which would permit continuous recovery of thedesired lower and higher molecular weight products. Fractionaldistillation may be employed in order to separate products.

Isomerization of the Intermediate and Final Products

It may be desirable to isomerize the intermediate or final paraffinproducts of this invention, increasing branching, octane value of thegasoline product and/or the low-temperature properties of the heavierproducts.

Isomerization processes are typically carried out at a temperature offrom 200° F. to 900° F. (93° C. to 482° C.), e.g., from 300° F. to 800°F. (149° C. to 427° C.), or from 400° F. to 800° F. (204° C. to 427°C.); a total reaction pressure of from 15 to 3000 psig (0.1 to 20.7 MPagauge), e.g., from 50 to 2500 psig (0.3 to 17.2 MPa gauge); a LHSV offrom 0.1 to 10 h⁻¹, e.g., from 0.25 to 5 h⁻¹; and a hydrogen gas treatrate of from 0.1 to 30 MSCF/bbl, e.g., from 0.2 to 20 MSCF/bbl, or from0.4 to 10 MSCF/bbl. Catalysts useful for isomerization processes aregenerally bifunctional catalysts that include a hydrogenation component(preferably selected from the Group VIII metals of the Periodic Table ofthe Elements, and more preferably selected from the group consisting ofnickel, platinum, palladium and mixtures thereof) and an acid component.Examples of an acid component useful in the preferred isomerizationcatalyst include a crystalline zeolite, a halogenated alumina component,or a silica-alumina component. Such paraffin isomerization catalysts arewell known in the art.

In some embodiments, the step of isomerizing is carried out using anisomerization catalyst. Suitable such isomerization catalysts caninclude, but are not limited to, Pt and/or Pd on a support. Suitablesupports include, but are not limited to, zeolites CIT-1, IM-5, SSZ-20,SSZ-23, SSZ-24, SSZ-25, SSZ-26, SSZ-31, SSZ-32, SSZ-32, SSZ-33, SSZ-35,SSZ-36, SSZ-37, SSZ-41, SSZ-42, SSZ-43, SSZ-44, SSZ-46, SSZ-47, SSZ-48,SSZ-51, SSZ-56, SSZ-57, SSZ-58, SSZ-59, SSZ-60, SSZ-61, SSZ-63, SSZ-64,SSZ-65, SSZ-67, SSZ-68, SSZ-69, SSZ-70, SSZ-71, SSZ-74, SSZ-75, SSZ-76,SSZ-78, SSZ-81, SSZ-82, SSZ-83, SSZ-86, SUZ-4, TNU-9, ZSM-5, ZSM-12,ZSM-22, ZSM-23, ZSM-35, ZSM-48, EMT-type zeolites, FAU-type zeolites,FER-type zeolites, MEL-type zeolites, MFI-type zeolites, MTT-typezeolites, MTW-type zeolites, MWW-type zeolites, TON-type zeolites, othermolecular sieves materials based upon crystalline aluminophosphates suchas SM-3, SM-7, SAPO-11, SAPO-31, SAPO-41, MAPO-11 and MAPO-31. In someembodiments, the step of isomerizing involves a Pt and/or Pd catalystsupported on an acidic support material selected from the groupconsisting of beta or zeolite Y molecular sieves, silica, alumina,silica-alumina, and combinations thereof. For other suitableisomerization catalysts, see, e.g., U.S. Pat. Nos. 4,859,312; 5,158,665;and 5,300,210.

With regard to the catalytic isomerization step described above, in someembodiments, the methods described herein can be conducted by contactingthe normal paraffins with a fixed stationary bed of catalyst, with afixed fluidized bed, or with a transport bed. In one embodiment, atrickle-bed operation is employed, wherein such feed is allowed totrickle through a stationary fixed bed, typically in the presence ofhydrogen. For an illustration of the operation of such catalysts, see,U.S. Pat. Nos. 6,204,426 and 6,723,889, the relevant disclosures areincorporated herein by reference.

In some embodiments, the isomerized product comprises at least 10 wt. %isoparaffins (e.g., at least 30 wt. %, 50 wt. %, or 70 wt. %isoparaffins). In some embodiments, the isomerized product has anisoparaffin to normal paraffin mole ratio of at least 5:1 (e.g., atleast 10:1, 15:1, or 20:1).

In some embodiments, the isomerized product has a boiling range of from250° F. to 1100° F. (121° C. to 593° C.), e.g., from 280° F. to 572° F.(138° C. to 300° C.), or from 250° F. to 1000° F. (121° C. to 538° C.).

In some embodiments, the isomerized product is suitable (or bettersuited) for use as a transportation fuel. In some such embodiments, theisomerized product is mixed or admixed with existing transportationfuels in order to create new fuels or to modify the properties ofexisting fuels. Isomerization and blending can be used to modulate andmaintain pour point and cloud point of the fuel or other product atsuitable values. In some embodiments, the normal paraffins are blendedwith other species prior to undergoing catalytic isomerization. In someembodiments, the normal paraffins are blended with the isomerizedproduct.

Other Processes for Altering the Product Stream

In a preferred embodiment, at least a portion of the C₆₊ product streamis reformed, for example using reforming conditions, to form aromaticproducts. Reforming is a complex process and involves a number ofcompeting processes or reaction sequences. These include dehydrogenationof cyclohexanes to aromatics, dehydroisomerization of alkylcyclopentanesto aromatics, and dehydrocyclization of acyclic hydrocarbons toaromatic. The hydrocracking of paraffins to light products boilingoutside the gasoline range and the dealkylation of alkylbenzenes areundesirable reactions in reforming processes. As the C₆₊ product streamincludes predominantly acyclic paraffins, the major reforming reactionis dehydrocyclization.

Conditions suitable for reforming C₆₊ product streams are well known inthe art. Representative reforming processes include the AROMAX™ processand platforming or rheniforming processes. The AROMAX™ process is wellknown to those of skill in the art, and is described, for example, inPetroleum & Petrochemical International, Volume 12, No. 12, pages 65 to68 (1972). Rheniforming processes are also well known to those of skillin the art, and are described, for example, in U.S. Pat. No. 3,415,737,the contents of which are hereby incorporated by reference. Theconventional reforming processes all tend to use catalysts that containPt and alumina, and frequently contain other elements such as rhenium,iridium, chlorine, fluorine and combinations thereof. Conventionalplatforming and rheniforming conditions may be preferred for C₇₊feedstocks, as they provide high yields and the catalysts are relativelystable. The AROMAX™ process is preferred for C₆-C₇ feedstocks, and tendsto give relatively high product yields.

These processes, their commercial startup conditions and their usefulrange of process operating conditions are all well known to thoseskilled in the art. These processes can be carried out in a singlereactor or in a series of reactors.

Unless otherwise indicated herein, scientific and technical terms usedin connection with the present invention shall have the meanings thatare commonly understood by those of ordinary skill in the art. Further,unless otherwise required by context, singular terms shall includepluralities and plural terms shall include the singular. Morespecifically, as used in this specification and the appended claims, thesingular forms “a”, “an” and “the” include plural referents unless thecontext clearly dictates otherwise. Thus, for example, reference to “afatty acid” includes a plurality of fatty acids, and the like. Inaddition, ranges provided in the specification and appended claimsinclude both end points and all points between the end points.Therefore, a range of 2.0 to 3.0 includes 2.0, 3.0 and all pointsbetween 2.0 and 3.0. Furthermore, all numbers expressing quantities,percentages or proportions, and other numerical values used in thespecification and claims, are to be understood as being modified in allinstances by the term “about”. As used herein, the term “include” andits grammatical variants are intended to be non-limiting, such thatrecitation of items in a list is not to the exclusion of other likeitems that can be substituted or added to the listed items. As usedherein, the term “comprising” means including elements or steps that areidentified following that term, but any such elements or steps are notexhaustive, and an embodiment can include other elements or steps.

EXAMPLES

The following illustrative examples are intended to be non-limiting. Thefollowing examples will help to further illustrate the invention but arenot intended to be a limitation on the scope of the process.

Example 1 Soybean Oil Feed

Soybean oil was purchased from Lucky Supermarket (El Cerrito, Calif.)under the Sunny Select brand. The soybean feed had an API gravity of21.6 (0.9223 g/mL). The triglycerides of soybean oil are derived mainlyfrom five fatty acids (see, e.g., S. Pinzi et al. Energy & Fuels, 2009,23, 2325-2341). Table 1 discloses the representative fatty acidcomposition of soybean oil.

TABLE 1 Fatty acid Carbon atoms:Double bonds Weight Percent Palmiticacid 16:0 11 Stearic acid 18:0 4 Oleic acid 18:1 24 Linoleic acid 18:254 α-Linoleic acid 18:3 7

Example 2 Canola Oil Feed

Canola oil was purchased from the Costco Warehouse (Richmond, Calif.)under the Superb brand. The Canola oil feed had an API gravity of 22.2(0.9197 g/mL). The triglycerides of Canola oil are derived mainly fromfive fatty acids according to literature. Table 2 discloses therepresentative fatty acid composition of Canola oil.

TABLE 2 Fatty acid Carbon atoms:Double bonds Weight Percent Palmiticacid 16:0 4 Stearic acid 18:0 2 Oleic acid 18:1 62 Linoleic acid 18:2 22α-Linoleic acid 18:3 10

Example 3 Molecular Redistribution Catalysts

The Molecular Redistribution catalyst employed for paraffindisproportionation in the present invention consisted of a physicalmixture of the following two catalysts:

(i) 0.5 wt. % Pt and 0.5 wt. % Li on amorphous Al₂O₃ and

(ii) 8.0 wt. % WO₃ on amorphous SiO₂.

These two catalysts were prepared from the 42-60 mesh particles of Al₂O₃or SiO₂ bases as described below:

(1) Preparation of 0.5 wt. % Pt and 0.5 wt. % Li on Al₂O₃:

0.3446 grams of Pt(NH₃)₄(NO₃)₂ and 1.7263 grams LiNO₃ were dissolved in49.0 grams of water. 34.4 grams of alumina (Condea, 42-60 mesh fraction)were impregnated with this solution at room temperature overnight. Theimpregnated particles were first dried in a vacuum oven at 250° F.overnight and then calcined in air initially at a temperature of 250° F.for 2 hours, subsequently raised to 700° F. over a period of 5 hours,and finally held at 700° F. for 8 hours. The catalyst was then cooled toroom temperature.

(2) Preparation of 8.0 wt. % WO₃ on SiO₂:

1.9886 grams of ammonium metatungstate (90.6 wt. % WO₃) were dissolvedin 48.0 grams of water. 20.72 grams of silica gel manufactured by W.R.Grace/Davison (silica gel grade 59, 42-60 mesh fraction) wereimpregnated with this solution at room temperature overnight. Theresulting impregnated particles were first dried in a vacuum oven at250° F. overnight and then calcined in the same manner as describedabove for Pt/Li/Al₂O₃ catalyst.

The Molecular Redistribution catalyst was prepared by mixing 2.3 mL ofthe aforementioned Pt/Li/Al₂O₃ catalyst and 1.7 mL of the aforementionedWO₃/SiO₂ catalyst. The homogenized catalyst mixture (4.0 mL totalcatalyst volume) had a volume ratio of 5:4 for Pt/Li/Al₂O₃ to WO₃/SiO₂.

In the flow type fixed bed catalytic experiments, the MolecularRedistribution catalyst (4.0 mL of total catalyst volume) prepared abovewas loaded into a ¼ inch stainless steel tube reactor which was mountedinto an electric furnace containing three heating zones. The catalystmixture was first dried in nitrogen flow (100 mL/min) at atmosphericpressure from room temperature to 400° F. within a period of one hourand held at 400° F. for one hour. The catalyst was then reduced inhydrogen flow (100 mL/min) using a temperature program consisting of400° F. to 900° F. within one hour and holding it at 900° F. for 12hours. Subsequently the catalyst was cooled down to 200° F. in the samehydrogen flow and then purged with a nitrogen flow (100 mL/min) forabout one hour. The nitrogen purge was necessary to remove the hydrogenpresent in the reactor system. The nitrogen was then switched to a feed(e.g., n-hexadecane, paraffins produced from soybean oil or Canola oilvia hydrotreating) delivered from an Isco pump. The reactor wassubsequently pressurized with the feed at 200° F. from the atmosphericpressure to a preset reaction pressure such as 500 or 1000 psig.

The Molecular Redistribution reaction was then started at a presetpressure (500 or 1000 psig) and a preset LHSV of 0.5 or 1.0 by using atemperature program from 200° F. to a preset temperature (e.g., 650 or750° F.) at a rate of 2° F./min. During the Molecular Redistributionreactions, no carrier gas such as H₂ or N₂ was added into the reactorsystem; only the feed went through the catalyst bed. The liquidMolecular Redistribution product produced at the preset LHSV (0.5 or1.0), the preset pressure (500 or 1000 psig) and the preset temperature(650 or 750° F.) was collected at room temperature as the effluent afterbeing depressurized from the reactor (500 or 1000 psig) to atmosphericpressure via a Kammer valve which was installed at the reactor exit tomaintain the reactor pressure.

The collected liquid Molecular Redistribution product was analyzed withan off-line GC and a GC-based simulated distillation (ASTM D-2887). Theeffluent was also analyzed with an on-line GC via a six-way samplingvalve every 3 hours. Very little amounts of gas products (methane andethane) were detected.

Example 4 Molecular Redistribution of n-Hexadecane

A Molecular Redistribution reaction experiment with normal hexadecane(n-C₁₆H₃₄) as feed was carried out over a Molecular Redistributioncatalyst of Example 3 (consisting of Pt/Li/Al₂O₃ and WO₃/SiO₂) at 650°F., 1000 psig and 0.5 LHSV. Both C15− and C17+ normal paraffins wereproduced. The conversion of n-hexadecane was 85 wt. %. The gaschromatographic results of the product are depicted in FIG. 1 (top).

Example 5 Molecular Redistribution of n-Eicosane

A Molecular Redistribution reaction experiment with normal eicosane(n-C₂₀H₄₂) as feed was carried out over a Molecular Redistributioncatalyst of Example 3 (consisting of Pt/Li/Al₂O₃ and WO₃/SiO₂) at 650°F., 1000 psig and 0.5 LHSV. Both C19− and C21+ normal paraffins wereproduced. The conversion of n-eicosane was 70 wt. %. The gaschromatographic results of the product are depicted in FIG. 1 (bottom).

Example 6 Molecular Redistribution of a Mixture of n-Hexadecane,n-Heptadecane, n-Octadecane, n-Nonadecane and n-Eicosane

A mixture was made of n-hexadecane (n-C₁₆H₃₄), n-heptadecane (n-C₁₇H₃₆),n-octadecane (n-C₁₈H₃₈), n-nonadecane (n-C₁₉H₄₀) and n-eicosane(n-C₂₀H₄₂), with each component in 20 wt. %. A Molecular Redistributionreaction experiment with this mixture as feed was carried out over aMolecular Redistribution catalyst of Example 3 (consisting ofPt/Li/Al₂O₃ and WO₃/SiO₂) at 650° F., 1000 psig and 0.5 LHSV. Both C15−and C21+ normal paraffins were produced. The gas chromatographic resultsof the feed and product are depicted in FIG. 2.

Example 7 Molecular Redistribution of n-Hexadecane

A Molecular Redistribution reaction experiment with normal hexadecane(n-C₁₆H₃₄) as feed was carried out over a Molecular Redistributioncatalyst of Example 3 (consisting of Pt/Li/Al₂O₃ and WO₃/SiO₂) at 750°F., 500 psig and 0.5 LHSV. Both C15− and C17+ normal paraffins wereproduced. The conversion of n-hexadecane was 75 wt. %. The gaschromatographic results of the n-hexadecane feed and its MolecularRedistribution product are depicted in FIG. 3. FIG. 4 shows thedistillation data (boiling point vs. volume %) of the n-hexadecane feedand its Molecular Redistribution product of this example, as determinedby the simulated distillation (ASTM D-2887 which is based on gaschromatography).

Example 8 Hydrotreating of Soybean Oil

The soybean oil feed from Example 1 was hydrotreated underhydroprocessing conditions in a single reactor over a promoted catalystbased on a Ni—Mo—W-maleate catalyst precursor (prepared as described inExample 1 of U.S. Pat. No. 7,807,599) and sulfided with dimethyldisulfide gas (as described in Example 6 of U.S. Pat. No. 7,807,599).The reactor conditions included a total reaction pressure of 1000 psig,600° F., a hydrogen gas rate of 8.0 MSCF/bbl, and an LHSV of 1.0 h⁻¹.

The composition of the liquid product from the hydrotreating of soybeanoil was determined by gas chromatography and is reported in FIG. 5(top). The major product components were n-pentadecane (n-C₁₅H₃₂),n-hexadecane (n-C₁₆H₃₄), n-heptadecane (n-C₁₇H₃₆) and n-octadecane(n-C₁₈H₃₈). The distillation data (boiling point vs. volume %) of theliquid product from the hydrotreating of soybean oil were also acquiredvia the simulated distillation (ASTM D-2887 which is based on gaschromatography) and are reported in FIG. 6.

Example 9 Molecular Redistribution of the Hydrotreating Product ofSoybean Oil

A Molecular Redistribution reaction experiment with the hydrotreatingproduct of soybean oil, produced in Example 8, was carried out over aMolecular Redistribution catalyst of Example 3 (consisting ofPt/Li/Al₂O₃ and WO₃/SiO₂) at 750° F., 500 psig and 0.5 LHSV. Thecomposition of the liquid product from Molecular Redistribution wasdetermined by gas chromatography and is reported in FIG. 5 (bottom).Both C14− and C19+ normal paraffins were produced. The conversion of thefeed was 41 wt. %. The distillation data (boiling point vs. volume %) ofthe liquid product from Molecular Redistribution were also acquired viathe simulated distillation (ASTM D-2887 which is based on gaschromatography) and are reported in FIG. 6.

Example 10 Hydroprocessing of Canola Oil via Hydrotreating andHydroisomerization

The Canola oil feed from Example 2 was hydroprocessed in two stages intwo serially connected reactors. The first reactor (at 600° F.)contained a promoted hydroprocessing catalyst prepared as disclosed inUS20090298677A1, e.g., an alumina-supported Ni—Mo catalyst availablefrom Chevron Lummus Global, having a median pore size of about 8 nm andspecific surface area of about 180 m²/g. The second reactor (at 650° F.)contained a Pt/SOPO-11 based hydroisomerization catalyst prepared asdisclosed in Example 3 of U.S. Pat. No. 5,939,349. The reactorconditions included a total reaction pressure of 1000 psig, a hydrogengas rate of 5.0 MSCF/bbl, and a total LHSV of 0.35 h⁻¹.

The composition of the liquid product from the hydrotreating andhydroisomerization of Canola oil was determined by gas chromatographyand is reported in FIG. 7 (top). The major product components wereiso-octadecanes (i-C₁₈H₃₈), iso-heptadecanes (i-C₁₂H₃₆) andiso-hexadecanes (i-C₁₆H₃₄), showing that the n-paraffins produced viahydrotreating of Canola oil in the first reactor were isomerized viahydroisomerization in the second reactor. The distillation data (boilingpoint vs. volume %) of the liquid product from the hydrotreating andhydroisomerization of Canola oil were also acquired via the simulateddistillation (ASTM D-2887 which is based on gas chromatography) and arereported in FIG. 8.

Example 11 Molecular Redistribution of theHydrotreating-Hydroisomerization Product of Canola Oil

A Molecular Redistribution reaction experiment with thehydrotreating-hydroisomerization product of Canola oil, produced inExample 10, was carried out over a Molecular Redistribution catalyst ofExample 3 (consisting of Pt/Li/Al₂O₃ and WO₃/SiO₂) at 750° F., 500 psigand 0.5 LHSV. Both C15− and C19+ paraffins were produced. Thecomposition of the liquid product from Molecular Redistribution wasdetermined by gas chromatography and is reported in FIG. 7 (bottom). Theconversion of the feed was 26 wt. %. Both lighter and heavier paraffinsrelative to the feed paraffins were produced. The distillation data(boiling point vs. volume %) of the liquid product from MolecularRedistribution were also acquired via the simulated distillation (ASTMD-2887 which is based on gas chromatography) and are reported in FIG. 8.

All patents, patent applications and publications are hereinincorporated by reference to the same extent as if each individualpatent, patent application or publication was specifically andindividually indicated to be incorporated by reference.

The present invention if not to be limited in scope by the specificembodiments described herein, which are intended as single illustrationsof individual aspects of the invention, and functionally equivalentmethods and components are within the scope of the invention. Indeed,various modifications of the invention, in addition to those shown anddescribed herein will become apparent to those skilled in the art fromthe foregoing description and accompanying drawings. Such modificationsare intended to fall within the scope of the appended claims.

What is claimed is:
 1. A process for the manufacture ofbiologically-derived paraffinic jet and diesel fuels, solvents and baseoils from a biological hydrocarbonaceous oxygenated oil, comprisingtriglycerides, comprising: (a) hydrotreating the biologicalhydrocarbonaceous oxygenated oil to form a first effluent mixturecomprising propane, carbon monoxide, carbon dioxide, water and an-paraffinic product; (b) recovering the n-paraffinic product from thefirst effluent mixture; and (c) converting the n-paraffinic product ofstep (b) over a paraffin disproportionation catalyst to form a secondeffluent mixture comprising a light n-paraffinic biologically derivedproduct and a heavy n-paraffinic biologically derived product.
 2. Theprocess of claim 1, further comprising: (d) recovering the lightn-paraffinic biologically derived product from step (c); and (e)recovering the heavy n-paraffinic biologically derived product from step(c).
 4. The process of claim 1, further comprising an isomerization stepof the n-paraffinic product from step (b).
 5. The process of claim 1,further comprising an isomerization step of the second effluent mixturefrom step (c).
 6. The process of claim 2, further comprising anisomerization step of the light n-paraffinic biologically derivedproduct, heavy n-paraffinic biologically derived product, or both thelight and heavy paraffinic biologically derived products.
 7. The processof claim 1, wherein the triglyceride is a mixture of triglycerides. 8.The process of claim 1, wherein the biological hydrocarbonaceousoxygenated oil is selected from the group consisting of rapeseed oil,colza oil, canola oil, tall oil, sunflower oil, soybean oil, hempseedoil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castoroil, coconut oil, lard, tallow and train oil.
 9. The process of claim 1,wherein step (c) further comprises: treatment of the n-paraffinicproduct of step (b) with a hydrogenation/dehydrogenation catalyst and anolefin metathesis catalyst under conditions which dehydrogenate theparaffins to olefins, metathesize the olefins, and hydrogenate theolefins to paraffins to provide a third effluent mixture comprising alight n-paraffinic biologically derived product and a heavy n-paraffinicbiologically derived product.
 10. The process of claim 9, wherein thehydrogenation/dehydrogenation catalyst includes at least one metal or acorresponding metal compound selected from the group consisting of iron,cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium andplatinum.
 11. The process of claim 10, wherein thehydrogenation/dehydrogenation catalyst comprises a metal orcorresponding metal compound selected from the group consisting of:rhenium, tin, germanium, gallium, indium, lead, tin and mixturesthereof.
 12. The process of claim 9, wherein the olefin metathesiscatalyst comprises a metal or corresponding metal compound is selectedfrom the group consisting of tungsten, molybdenum, tin and rhenium. 13.The process of claim 12, wherein the olefin metathesis catalystcomprises tungsten.
 14. The process of claim 9, wherein thehydrogenation/dehydrogenation catalyst comprises platinum or a platinumcompound and the olefin metathesis catalyst comprises tungsten.
 15. Theprocess of claim 14, wherein the hydrogenation/dehydrogenation catalystis platinum-on-alumina and the olefin metathesis catalyst istungsten-on-silica and the volumetric ratio of the platinum component tothe tungsten component is greater than 1:50 and less than 50:1, andwherein the amount of platinum on the alumina is within the range offrom about 0.01 weight percent to about 10 weight percent on anelemental basis and the amount of tungsten on the silica is within therange of from about 0.01 weight percent to about 50 weight percent on anelemental basis.
 16. The process of claim 15, wherein the volumetricratio of the platinum component to the tungsten component is between1:10 and 10:1 and wherein the amount of platinum on the alumina iswithin the range of from about 0.1 weight percent to about 5.0 weightpercent on an elemental basis and the amount of tungsten on the silicais within the range of from about 0.1 weight percent to about 20 weightpercent on an elemental basis.
 17. The process of claim 9, wherein step(c) further comprises a temperature between about 400° F. to 1000° F.18. The process of claim 9, wherein step (c) further comprises apressure between about 50 psig to 3000 psig.
 19. The process of claim 9,wherein step (c) further comprises a liquid hourly space velocitybetween about 0.1 to 5 h⁻¹.
 20. The process of claim 1, wherein step (a)further comprises a temperature for hydrotreating between about 300° F.to 750° F.
 21. The process of claim 1, wherein step (a) furthercomprises a total reaction pressure for hydrotreating between about 50to 3000 psig.
 22. The process of claim 1, wherein step (a) furthercomprises a liquid hourly space velocity for hydrotreating between about0.1 to 5 h⁻¹.
 23. The process of claim 1, wherein step (a) furthercomprises a hydrogen feed rate for hydrotreating between about 0.1 to 20MSCF/bbl.